WO2016104294A1 - Encre à base d'eau - Google Patents

Encre à base d'eau Download PDF

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Publication number
WO2016104294A1
WO2016104294A1 PCT/JP2015/085262 JP2015085262W WO2016104294A1 WO 2016104294 A1 WO2016104294 A1 WO 2016104294A1 JP 2015085262 W JP2015085262 W JP 2015085262W WO 2016104294 A1 WO2016104294 A1 WO 2016104294A1
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WO
WIPO (PCT)
Prior art keywords
water
mass
less
based ink
pigment
Prior art date
Application number
PCT/JP2015/085262
Other languages
English (en)
Japanese (ja)
Inventor
要 光吉
泰陽 竹野
鈴木　啓之
貴裕 吉川
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to US15/539,370 priority Critical patent/US10316207B2/en
Priority to EP15872863.4A priority patent/EP3239255B1/fr
Priority to CN201580067619.7A priority patent/CN107001835B/zh
Priority to KR1020177016220A priority patent/KR20170100506A/ko
Publication of WO2016104294A1 publication Critical patent/WO2016104294A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant

Definitions

  • the present invention relates to a water-based ink and an ink jet recording method using the water-based ink.
  • Water-based inks are widely used as inks for flexographic printing, gravure printing, and inkjet recording.
  • the ink jet recording method is a recording method in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle onto a recording medium and attaching them. This method is widely spread because it is easy to make full color and is inexpensive, and has many advantages such as the ability to use plain paper as a recording medium and non-contact with the substrate.
  • ink for ink jet recording using a pigment as a colorant and resin fine particles as a binder is used in an ink jet recording system.
  • surfactants and organic solvents are used in water-based inks for inkjet recording in order to make them suitable for nozzle heads and to obtain high quality printed matter.
  • JP-T-2006-524269 discloses an ink jet containing an effective amount of latex fine particles having a specific bulk density and a specific surface dielectric constant, and a surfactant adsorbed on the surface of the latex fine particles.
  • An ink has been disclosed, and it has been shown that it has excellent dispersion stability and printability.
  • Patent Document 2 discloses an ink jet recording in which a mixture containing a colorant, a nonionic organic compound in a polymer particle, a water-soluble surfactant, and water is heated at 40 ° C. or higher.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2006-282759
  • Patent Document 3 includes a water-insoluble vinyl polymer particle that includes a pigment and that allows the pigment to be dispersed in the ink composition, a surfactant, and water.
  • An ink composition is disclosed in which the surfactant contains acetylene glycol and an ethylene oxide adduct of acetylene glycol in a specific weight ratio, and is excellent in color development on plain paper and gloss on glossy paper, and is ejected.
  • Patent Document 4 discloses at least a water-insoluble colorant, glycol ethers having an HLB value of 4.2 to 8.0, and 1,2-alkyl having 4 to 8 carbon atoms.
  • An aqueous ink composition comprising a diol, resin particles, water, and further a silicone surfactant and / or an acetylene glycol surfactant is disclosed, and is used as a non-ink-absorbing or low-absorbing recording medium.
  • an image having excellent print quality and abrasion resistance can be formed.
  • Patent Document 5 discloses an ink composition for ink-jet recording containing a pigment, a water-soluble organic solvent, and a penetrant, and a 1,2-alkane as the water-soluble organic solvent.
  • a composition containing an alkyl ether derivative having 3 or more carbon atoms of diol and glycol, and containing a specific polysiloxane surfactant and a specific acetylene glycol surfactant as a penetrating agent is disclosed. It is described that generation of rainbow unevenness in an image can be suppressed.
  • Patent Document 6 JP-A-2006-282810 discloses an ink composition containing a solid solution pigment composed of two or more quinacridone compounds, a polyether-modified polydimethylsiloxane compound, and water. It is described that a color image can be realized and discharge stability is excellent.
  • Patent Document 7 discloses an ink composition containing three or more acetylene glycol surfactants, a coloring material, and water, and the total content of acetylene glycol surfactants.
  • An ink composition for inkjet recording which is 0.1 to 3% by mass with respect to the total mass of the ink composition, is disclosed, and is described as being capable of recording an image with excellent image quality and fixability at high speed. Yes.
  • low-water-absorbent coated paper such as offset coated paper, or polyvinyl chloride resin, polypropylene resin, polyester resin, etc. Printing on a recording medium for commercial printing which has been surface-treated with a non-water-absorbing synthetic resin film has been demanded.
  • the present invention includes a pigment, a water-insoluble polymer, an acetylene glycol-based nonionic surfactant (A) having an HLB of 0 to 5, and a nonionic surfactant (B) having an HLB of 6 to 20.
  • the present invention relates to a water-based ink containing a polyether-modified silicone (C) having a kinematic viscosity at 25 ° C. of 30 mm 2 / s to 190 mm 2 / s and an organic solvent (D) having a specific boiling point.
  • the dot diameter of the ink may be reduced during the drying process of the ink on the recording medium, particularly the non-ink-absorbing or low-absorbing recording medium. This is not satisfactory in terms of the uniformity of subsequent images.
  • the present invention provides a water-based ink that is excellent in dischargeability and suppresses the reduction of the dot diameter of the ink in the drying process even when printed on a low water-absorbing recording medium, and that provides an image with excellent uniformity, and the water-based ink
  • the present invention relates to an ink jet recording method using ink.
  • the present inventors include a pigment, a water-insoluble polymer, two types of nonionic surfactants (A) and (B) having different HLB values, a polyether-modified silicone (C) having a specific kinematic viscosity, It has been found that an aqueous ink containing an organic solvent (D) having a specific boiling point can solve the above problems. That is, the present invention relates to the following [1] and [2].
  • a water-based ink having a temperature of 230 ° C. or lower.
  • an aqueous system that is excellent in ejection properties, suppresses the reduction of the ink dot diameter during the drying process even when printed on a recording medium, particularly a low water-absorbing recording medium, and provides an image with excellent uniformity.
  • An ink and an ink jet recording method using the water-based ink can be provided.
  • “low water absorption” is a concept including low water absorption and non-water absorption of water and / or ink. More specifically, the contact time between the recording medium and pure water is 100 milliseconds. It means that the water absorption amount of the recording medium is from 0 g / m 2 to 10 g / m 2 .
  • the water-based ink of the present invention includes a pigment, a water-insoluble polymer, and an acetylene glycol-based nonionic surfactant (A) having an HLB of 0 or more and 5 or less (hereinafter also simply referred to as “nonionic surfactant (A)”). ), A nonionic surfactant (B) having an HLB of 6 or more and 20 or less (hereinafter also referred to simply as “nonionic surfactant (B)”), and a kinematic viscosity at 25 ° C.
  • polyether-modified silicone (hereinafter also simply referred to as “polyether-modified silicone (C)”) and an organic solvent (D), and a weighted average value of boiling points of the organic solvent (D) Is 150 ° C. or higher and 230 ° C. or lower.
  • water-based ink for inkjet recording, but can also be used for flexographic printing and gravure printing.
  • “Aqueous” means that water occupies the largest proportion of the medium contained in the ink. In some cases, the medium is only water, and water and one or more organic solvents are used. In the case of a mixed solvent of
  • the water-based ink of the present invention has excellent ejection properties, and even when printed on a low-water-absorbing recording medium, the dot diameter of the ink during the drying process is suppressed and an image with excellent uniformity can be obtained.
  • the reason is not clear, but it is thought as follows.
  • ink jet recording printing
  • the water-based ink is not absorbed into the recording medium but stays on the recording medium as droplets.
  • the acetylene glycol-based nonionic surfactant (A) having an HLB of 0 or more and 5 or less reduces the surface tension of the water-based ink and promotes the spreading of the droplet on the recording medium.
  • the modified silicone (C) suppresses shrinkage of the dot diameter of the droplet during the drying process by orienting on the surface of the droplet after wetting and spreading.
  • the kinematic viscosity of the polyether-modified silicone (C) is considered to be an indicator of orientation on the droplet surface in the course of wetting and drying.
  • the nonionic surfactant (B) having an HLB of 6 or more and 20 or less is estimated to stably disperse the nonionic surfactant (A) and the polyether-modified silicone (C) in the water-based ink.
  • the surfactant is concentrated on the nozzle surface.
  • the water-based ink can be prevented from drying, and hence it is considered that the discharge property is excellent.
  • an organic solvent (D) image uniformity due to spreading of dots when printing on a low water-absorbing recording medium by the ink jet recording method is improved, and drying of the ink in the ink jet nozzle is prevented. Therefore, it is considered that the discharge property is improved.
  • the water-based ink of the present invention comprises a pigment, a water-insoluble polymer, a nonionic surfactant (A), a nonionic surfactant (B), a polyether-modified silicone (C), and an organic solvent (D). Containing.
  • A nonionic surfactant
  • B nonionic surfactant
  • C polyether-modified silicone
  • D organic solvent
  • a pigment is used as a colorant from the viewpoint of improving the water resistance and weather resistance of the printed matter.
  • the pigment is not particularly limited and can be used in the form of (i) a self-dispersing pigment, (ii) a pigment dispersed with a water-soluble polymer, (iii) water-insoluble polymer particles containing the pigment, and the like. In these, it is preferable to use a pigment as the water-insoluble polymer particle containing (iii) a pigment.
  • water-insoluble polymer particles Q described later are used as the water-insoluble polymer used in the ink of the present invention.
  • the pigment used in the present invention may be either an inorganic pigment or an organic pigment. If necessary, they can be used in combination with extender pigments.
  • the inorganic pigment include carbon black, metal oxide, metal sulfide, and metal chloride. Of these, carbon black is preferred particularly for black aqueous inks. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.
  • organic pigment examples include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments.
  • the hue is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, blue, red, orange, and green can be used.
  • Specific examples of preferred organic pigments include C.I. I. Pigment yellow, C.I. I. Pigment Red, C.I. I. Pigment orange, C.I. I. Pigment violet, C.I. I. Pigment blue, and C.I. I.
  • extender pigments include silica, calcium carbonate, and talc. The above pigments can be used alone or in admixture of two or more.
  • the content of the pigment in the water-based ink is intended to improve the print density when printing on a highly water-absorbing medium, and accelerates the drying on the paper surface when printing on a low water-absorbing recording medium. From the viewpoint of improving the ratio, it is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more.
  • the ink density at the time of solvent volatilization is lowered, the reduction of the ink dot diameter during the drying process when printing on a low water-absorbing recording medium is suppressed, and the printing density is increased from the viewpoint of obtaining an image with excellent uniformity.
  • the pigment can be used as an aqueous dispersion, and the blending amount when blending the pigment aqueous dispersion into the water-based ink can be determined so that the pigment content falls within the above range.
  • Self-dispersing pigments that can be used in the present invention are hydrophilic functional groups (anionic hydrophilic groups such as carboxy groups and sulfonic acid groups, or cationic hydrophilic groups such as quaternary ammonium groups). 1) or more of the group) can be dispersed in an aqueous medium without using a surfactant or resin by bonding to the surface of the pigment directly or through other atomic groups such as alkanediyl groups having 1 to 12 carbon atoms. It means a pigment that is possible. In order to make the pigment a self-dispersing pigment, for example, a necessary amount of the hydrophilic functional group may be chemically bonded to the pigment surface by a conventional method.
  • self-dispersing pigments include CAB-O-JET 200, 300, 352K, 250C, 260M, 270Y, 450C, 465M, 470Y, 480V (manufactured by Cabot) and BONJET.
  • CW-1, CW-2 manufactured by Orient Chemical Co., Ltd.
  • Aqua-Black 162 manufactured by Tokai Carbon Co., Ltd.
  • SDP-100, SDP-1000, SDP-2000 manufactured by SENSIENT
  • the self-dispersing pigment is preferably used as an aqueous dispersion dispersed in water.
  • the pigment dispersed with the water-soluble polymer is preferably an aqueous dispersion in which the pigment is dispersed with the water-soluble polymer.
  • the water-soluble polymer include a copolymer having a carboxyl group including acrylic acid or methacrylic acid.
  • examples of commercially available water-soluble polymers include JONCRYL67, 678, 683, and 60J.
  • the pigment dispersed with the water-soluble polymer is preferably used as an aqueous dispersion containing the pigment dispersed by adding a pigment to water in which the water-soluble polymer is dissolved and applying a shear stress.
  • Examples of means for applying a shear stress include a kneader such as a roll mill and a kneader, a high-pressure homogenizer such as a microfluidizer (manufactured by Microfluidics), a media type dispersing machine such as a paint shaker and a bead mill.
  • Examples of commercially available media type dispersers include Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.), Pico Mill (manufactured by Hirota Iron Works Co., Ltd.), and the like. A plurality of these devices can be combined.
  • the water-based ink of the present invention preferably contains water-insoluble polymer particles from the viewpoint of fixability when printing on a low water-absorbing recording medium.
  • the nonionic surfactant (A), nonionic surfactant (B), and polyether-modified silicone (C) contained in the ink of the present invention improve the dispersion stability of insoluble polymer particles in water-based ink. It is excellent in dischargeability.
  • the pigment and the water-insoluble polymer are water-insoluble polymer particles containing a pigment (hereinafter referred to as “pigment-containing polymer”).
  • the form of the pigment-containing polymer particles P is not particularly limited as long as the particles are formed of at least the pigment and the water-insoluble polymer p.
  • a particle form in which a pigment is encapsulated in the water-insoluble polymer p, a particle form in which the pigment is uniformly dispersed in the water-insoluble polymer p, a particle form in which the pigment is exposed on the surface of the water-insoluble polymer particle p, And mixtures thereof are also included.
  • the water-insoluble polymer p constituting the pigment-containing polymer particle P has a function as a dispersant for dispersing the pigment in the aqueous medium and maintaining the dispersion stably, and a function as a fixing agent for the recording medium.
  • the water-insoluble polymer means a polymer that is dried for 2 hours at 105 ° C. and reaches a constant weight, and when it is dissolved in water, it settles without dissolving in water or the particle size is detected.
  • a polymer in which a particle size of preferably 20 nm or more, more preferably 50 nm or more is observed.
  • the water-insoluble polymer is an anionic polymer
  • the solubility is judged in a state where the anionic group of the polymer is neutralized with sodium hydroxide 100%.
  • polymers used include polyesters, polyurethanes, and vinyl polymers. From the viewpoint of improving the storage stability of ink, vinyl polymers obtained by addition polymerization of vinyl monomers (vinyl compounds, vinylidene compounds, vinylene compounds). Polymers are preferred.
  • the water-insoluble polymer p includes a structural unit derived from the ionic monomer (p-1), a structural unit derived from the hydrophobic monomer (p-2) having an aromatic ring, and a hydrophilic property represented by the formula (1) described later.
  • the water-insoluble polymer p includes, for example, an ionic monomer (p-1), a hydrophobic monomer (p-2) having an aromatic ring, and a hydrophilic nonionic monomer (p-) represented by the formula (1) described later. 3) can be obtained by addition polymerization by a known method.
  • the ionic monomer (p-1) is used for the dispersion stability of the pigment aqueous dispersion during the production of the “aqueous dispersion of pigment-containing polymer particles P” (hereinafter also referred to as “pigment aqueous dispersion”). From the viewpoint of improving the storage stability of the water-based ink, it is used as a monomer component of the water-insoluble polymer p.
  • the ionic monomer (p-1) include an anionic monomer and a cationic monomer. From the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the water-based ink, and the viewpoint of improving the dischargeability.
  • an anionic monomer is preferable.
  • the ionic monomer includes a monomer that becomes an ion under acidic or alkaline conditions, even if it is a neutral non-ionic monomer such as an acid or an amine compound.
  • an anionic monomer 1 or more types chosen from a carboxylic acid monomer, a sulfonic acid monomer, a phosphoric acid monomer, etc. are mentioned.
  • the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
  • Examples of the sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 3-sulfopropyl (meth) acrylate.
  • Examples of the phosphoric acid monomer include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like.
  • (meth) acrylate means 1 or more types chosen from a methacrylate and an acrylate. The same applies to the following.
  • Examples of the cationic monomer include one or more selected from unsaturated tertiary amine-containing vinyl monomers and unsaturated ammonium salt-containing vinyl monomers.
  • unsaturated tertiary amine-containing monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethyl.
  • Examples include aminopropyl (meth) acrylamide, N, N-dimethylarylamine, vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-6-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like.
  • Examples of the unsaturated ammonium salt-containing monomer include N, N-dimethylaminoethyl (meth) acrylate quaternized product, N, N-diethylaminoethyl (meth) acrylate quaternized product, N, N-dimethylaminopropyl (meth) acrylate quaternary product. And the like.
  • the cationic monomers N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide and vinyl pyrrolidone are preferable.
  • Hydrophobic monomer (p-2) having an aromatic ring is effective in improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the water-based ink. It is used from the viewpoint of improving.
  • hydrophobic monomer (p-2) having an aromatic ring include one or more selected from styrene monomers, aromatic group-containing (meth) acrylates, and styrene macromonomers.
  • styrene monomer styrene and 2-methylstyrene are preferable from the same viewpoint as described above, and styrene is more preferable.
  • the aromatic group-containing (meth) acrylate from the same viewpoint as above, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable, and benzyl (meth) acrylate is more preferable.
  • the styrenic macromonomer is a compound having a polymerizable functional group at one end and a number average molecular weight of 500 or more and 100,000 or less. From the same viewpoint as described above, the number average molecular weight is preferably 1,000 or more, more preferably. It is 2,000 or more, more preferably 3,000 or more, and preferably 10,000 or less, more preferably 9,000 or less, and still more preferably 8,000 or less.
  • the number average molecular weight is a value measured using polystyrene as a standard substance by gel permeation chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent.
  • examples of commercially available styrenic macromonomers include AS-6 (S), AN-6 (S), HS-6 (S) (trade name of Toagosei Co., Ltd.), and the like.
  • As the hydrophobic monomer (p-2) having an aromatic ring two or more selected from styrene monomers, aromatic group-containing (meth) acrylates, and styrene macromonomers are used in combination from the same viewpoint as described above. It is more preferable that styrene or benzyl (meth) acrylate and a styrenic macromonomer are used in combination.
  • hydrophilic nonionic monomer represented by formula (1) (p-3) The hydrophilic nonionic monomer (p-3) represented by the formula (1) suppresses thickening at the time of drying the aqueous ink from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the aqueous ink. This is used from the viewpoint of improving dischargeability.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a hydrogen atom substituted with an alkyl group having 1 to 9 carbon atoms.
  • a good phenyl group is shown
  • m shows an average added mole number, and is a number of 2 or more and 100 or less.
  • R 1 is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the water-based ink.
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the water-based ink. More preferably, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is still more preferable.
  • m is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and m is preferably from the viewpoint of improving the storage stability and dischargeability of the water-based ink. 50 or less, more preferably 20 or less, still more preferably 10 or less.
  • the monomer (p-3) represented by the above formula (1) include polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol mono (meth) acrylate, and stearoxypolyethylene glycol.
  • mono (meth) acrylate and the like can be mentioned, and methoxypolyethylene glycol mono (meth) acrylate is more preferable.
  • Specific examples of commercially available monomers represented by the formula (1) include NK ester M-20G, M-23G, M-40G, M-60G, M-90G, M- 230G, M-450G, M-900G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Bremer PME-200 (produced by NOF Corporation), Light Ester MTG, Light Ester 041MA (above, manufactured by Kyoeisha Chemical Co., Ltd.) ) And the like.
  • the monomers (p-1), (p-2) and (p-3) can be used alone or in admixture of two or more.
  • the water-insoluble polymer p used in the present invention contains structural units derived from monomers other than the monomers (p-1), (p-2) and (p-3) as long as the object of the present invention is not impaired. can do.
  • Other monomers include alkyl (meth) acrylates having 1 to 22 carbon atoms such as methyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. And the like, and silicone-based macromonomers such as organopolysiloxane having a polymerizable functional group at one end, and the like.
  • the content of the structural unit derived from the components (p-1), (p-2) and (p-3) in the water-insoluble polymer p is the pigment aqueous dispersion. From the viewpoint of improving the dispersion stability of the water-based ink and the storage stability of the water-based ink, and from the viewpoint of improving dischargeability by suppressing the viscosity increase when the water-based ink is dried, it is as follows.
  • the content thereof is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and still more preferably 10% by mass or more. Yes, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.
  • the hydrophobic monomer (p-2) having an aromatic ring is contained, the content thereof is preferably 15% by mass or more, more preferably 30% by mass or more, further preferably 37% by mass or more, and still more preferably.
  • the styrene macromonomer is included as the monomer (p-2), the styrenic macromonomer and the other monomer (p-2) such as a styrene monomer and / or an aromatic group-containing (meth) acrylate It is preferable to use together.
  • the content of the styrenic macromonomer is preferably 5% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less. More preferably, it is 30% by mass or less.
  • the content thereof is preferably 13% by mass or more, more preferably 15% by mass or more, still more preferably 18% by mass or more, and still more preferably 20% by mass. And more preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 38% by mass or less, and still more preferably 35% by mass or less.
  • the mass ratio is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.10 or more, from the viewpoint of improving the dispersion stability of the pigment water dispersion and the storage stability of the water-based ink. And preferably it is 0.50 or less, More preferably, it is 0.40 or less, More preferably, it is 0.30 or less.
  • the water-insoluble polymer p is produced by copolymerizing the monomer mixture by a known polymerization method.
  • a solution polymerization method is preferable.
  • a polymerization initiator or a polymerization chain transfer agent can be used.
  • the polymerization initiator an azo compound is more preferable, and 2,2′-azobis (2,4-dimethylvaleronitrile) is more preferable.
  • the polymerization chain transfer agent mercaptans are preferable, and 2-mercaptoethanol and the like are more preferable.
  • the polymerization temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and the polymerization time is preferably 1 hour or longer and 20 hours or shorter.
  • the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
  • the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation. The obtained polymer can remove unreacted monomers and the like by reprecipitation, membrane separation, chromatographic method, extraction method and the like.
  • the water-insoluble polymer p is a polymer solution as it is because the organic solvent a contained therein is used as the organic solvent b described later without removing the solvent used in the polymerization reaction. It is preferable to use as.
  • the solid content concentration of the water-insoluble polymer p solution is preferably 25% by mass or more, more preferably 30% by mass or more, and preferably 60% by mass or less. More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less.
  • the weight average molecular weight of the water-insoluble polymer p used in the present invention is preferably 10,000 or more, more preferably 15,000 or more, from the viewpoint of improving the dispersion stability of the pigment water dispersion and the storage stability of the water-based ink. More preferably, it is 20,000 or more, and still more preferably 30,000 or more. Further, from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and the storage stability of the water-based ink, and from the viewpoint of improving dischargeability by suppressing the viscosity increase when the water-based ink is dried, preferably 150,000 or less, More preferably, it is 100,000 or less.
  • the weight average molecular weight of the water-insoluble polymer p can be measured by the method described in the examples.
  • the pigment-containing polymer particles P are preferably produced as an aqueous dispersion (pigment water dispersion) of the pigment-containing polymer particles P from the viewpoint of improving the productivity of the water-based ink.
  • the pigment water dispersion can be obtained by a method having the following steps (1) and (2).
  • Step (1) A step of dispersing a mixture containing water-insoluble polymer p, organic solvent b, pigment, and water (hereinafter also referred to as “pigment mixture”) to obtain a dispersion-treated product
  • Step (2) Step A step of removing the organic solvent b from the dispersion-treated product obtained in (1) to obtain a pigment aqueous dispersion
  • Step (1) is a step of obtaining a dispersion-treated product by subjecting a mixture (pigment mixture) containing water-insoluble polymer p, organic solvent b, pigment, and water to a dispersion treatment.
  • a pigment mixture it is preferable to first obtain a pigment mixture by mixing a water-insoluble polymer p, an organic solvent b, a pigment, water, and, if necessary, a neutralizing agent and a surfactant.
  • the order of addition is not limited, but the water-insoluble polymer p, the organic solvent b, the neutralizing agent, water, and the pigment are preferably added in this order.
  • organic solvent b Although there is no restriction
  • the solvent used in the polymerization can be used as it is.
  • the mass ratio of the water-insoluble polymer p to the organic solvent b [water-insoluble polymer p / organic solvent b] is 0.10 or more from the viewpoint of improving the wettability to the pigment and the adsorptivity of the water-insoluble polymer p to the pigment. Is preferable, 0.15 or more is more preferable, 0.20 or more is more preferable, 0.70 or less is preferable, 0.60 or less is more preferable, and 0.50 or less is further preferable.
  • a neutralizing agent can be used from the viewpoint of improving the dispersion stability of the pigment water dispersion, the storage stability of the water-based ink, and the dischargeability.
  • the pH of the pigment aqueous dispersion is preferably 7 or more, more preferably 7.5 or more, and the pH is preferably 11 or less, more preferably 9.5 or less. It is preferable to neutralize.
  • the neutralizing agent include alkali metal hydroxides, ammonia, and organic amines.
  • the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide, and sodium hydroxide is preferable.
  • the organic amine examples include trimethylamine, ethylamine, diethylamine, triethylamine, and triethanolamine.
  • the neutralizing agent is preferably an alkali metal hydroxide or ammonia from the viewpoint of improving the dispersion stability of the pigment water dispersion, the storage stability of the water-based ink, and the ejection property, and sodium hydroxide and ammonia may be used in combination. More preferred. Further, the water-insoluble polymer p may be neutralized in advance.
  • the neutralizing agent is preferably used as an aqueous neutralizing agent solution from the viewpoint of sufficiently and uniformly promoting neutralization.
  • the concentration of the neutralizing agent aqueous solution is preferably 3% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, more preferably 30% by mass or less, and preferably 25% by mass or less. More preferred.
  • the weight ratio of the neutralizing agent aqueous solution to the organic solvent b increases the adsorptivity of the water-insoluble polymer p to the pigment and neutralization of the polymer to promote the dispersion stability of the pigment dispersion and From the viewpoint of storage stability of water-based ink, reduction of coarse particles, and improvement of water-based ink discharge performance, 0.01 or more is preferable, 0.05 or more is more preferable, 0.10 or more is more preferable, and 0. 50 or less is preferable, 0.30 or less is more preferable, and 0.20 or less is still more preferable. You may use a neutralizing agent and neutralizing agent aqueous solution individually or in mixture of 2 or more types.
  • the degree of neutralization of the water-insoluble polymer p is preferably 30 mol% or more from the viewpoint of improving the dispersion stability of the pigment water dispersion and the storage stability of the water-based ink, the reduction of coarse particles, and the dischargeability of the water-based ink. More preferably, mol% or more is more preferable, 50 mol% or more is more preferable, 300 mol% or less is preferable, 200 mol% or less is more preferable, and 150 mol% or less is still more preferable.
  • the degree of neutralization with an alkali metal hydroxide is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 It is more preferably at least mol%, more preferably at most 150 mol%, more preferably at most 125 mol%, further preferably at most 100 mol%.
  • the neutralization degree is obtained by dividing the molar equivalent of the neutralizing agent by the molar amount of the anionic group of the water-insoluble polymer p.
  • the content of the pigment is 10% by mass or more in the pigment mixture from the viewpoint of improving the dispersion stability of the pigment water dispersion, the storage stability of the system ink, and the dischargeability, and the productivity of the pigment water dispersion. 12 mass% or more is more preferable, 14 mass% or more is more preferable, and 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable.
  • the content of the water-insoluble polymer p is preferably 2.0% by mass or more in the pigment mixture from the viewpoint of improving the dispersion stability of the pigment water dispersion, the storage stability of the water-based ink, and the ejection property.
  • % Or more is more preferable, 5.0 mass% or more is more preferable, 15 mass% or less is preferable, 10 mass% or less is more preferable, and 8.0 mass% or less is still more preferable.
  • the content of the organic solvent b is preferably 10% by mass or more, more preferably 12% by mass or more in the pigment mixture from the viewpoint of improving the wettability to the pigment and the adsorptivity of the water-insoluble polymer p to the pigment. % By mass or more is more preferable, and 35% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is more preferable.
  • the water content is preferably 40% by mass or more, more preferably 45% by mass or more in the pigment mixture from the viewpoint of improving the dispersion stability of the pigment water dispersion and improving the productivity of the pigment water dispersion. 50 mass% or more is more preferable, 75 mass% or less is preferable, 70 mass% or less is more preferable, and 65 mass% or less is still more preferable.
  • the mass ratio of the pigment to the water-insoluble polymer p [pigment / water-insoluble polymer p] is preferably 0.4 or more from the viewpoint of lowering the ink viscosity at the time of solvent volatilization and improving the storage stability and ejection property of the water-based ink. 1 or more is more preferable, 1.5 or more is more preferable, 9 or less is preferable, 6 or less is more preferable, and 4 or less is still more preferable.
  • step (1) the pigment mixture is further dispersed to obtain a dispersion-treated product.
  • a dispersion-treated product There is no restriction
  • the average particle size of the pigment particles can be atomized only by the main dispersion until the desired particle size is reached, preferably the pigment mixture is pre-dispersed and further subjected to shear stress to perform the main dispersion. It is preferable to control the average particle size of the particles so as to have a desired particle size.
  • the temperature in the preliminary dispersion in step (1) is preferably 0 ° C. or higher, preferably 40 ° C. or lower, more preferably 30 ° C.
  • the dispersion time is preferably 0.5 hours or longer, 1 hour or more is more preferable, 30 hours or less is preferable, 10 hours or less is more preferable, and 5 hours or less is still more preferable.
  • a commonly used mixing and stirring device such as an anchor blade or a disper blade can be used.
  • the mixing and stirring devices a high-speed stirring and mixing device is preferable.
  • the temperature in the main dispersion in the step (1) is preferably 0 ° C. or higher, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and further preferably 20 ° C. or lower.
  • means for applying the shear stress of this dispersion include kneaders such as roll mills and kneaders, high-pressure homogenizers such as microfluidizers (manufactured by Microfluidics), media-type dispersers such as paint shakers and bead mills.
  • Examples of commercially available media type dispersers include Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.), Pico Mill (manufactured by Hirota Iron Works Co., Ltd.), and the like. A plurality of these devices can be combined. Among these, it is preferable to use a high-pressure homogenizer from the viewpoint of reducing the particle size of the pigment. When this dispersion is performed using a high-pressure homogenizer, the pigment can be controlled to have a desired particle size by controlling the processing pressure and the number of passes.
  • the processing pressure is preferably 60 MPa or more, more preferably 100 MPa or more, further preferably 130 MPa or more, more preferably 200 MPa or less, more preferably 180 MPa or less, and still more preferably 170 MPa or less, from the viewpoints of productivity and economy.
  • the number of passes is preferably 3 times or more, more preferably 5 times or more, still more preferably 7 or more, and preferably 30 times or less, more preferably 25 times or less, and even more preferably 15 times or less. .
  • Step (2) is a step of removing the organic solvent b from the dispersion treated product obtained in step (1) to obtain a pigment water dispersion.
  • the removal of the organic solvent b can be performed by a known method. Before removing the organic solvent b from the viewpoint of suppressing the generation of aggregates in the process of removing the organic solvent b and improving the dispersion stability of the pigment aqueous dispersion, the storage stability of the water-based ink, and the discharge performance. It is preferable to adjust the mass ratio of organic solvent b to water (organic solvent b / water) by adding water to the dispersion-treated product obtained in step (1).
  • the mass ratio of (organic solvent b / water) is preferably 0.08 or more, more preferably 0.10 or more, and preferably 0.40 or less, more preferably 0.20 or less.
  • the non-volatile component concentration (solid content concentration) of the pigment aqueous dispersion after adjusting the mass ratio (organic solvent b / water) is a viewpoint that suppresses the generation of aggregates in the process of removing the organic solvent b, and the pigment. From the viewpoint of improving the productivity of the aqueous dispersion, it is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, more preferably 30% by mass or less, and more preferably 25% by mass or less. Preferably, 20 mass% or less is more preferable. A part of the water contained in the pigment aqueous dispersion may be removed simultaneously with the organic solvent b.
  • Examples of the apparatus for removing the organic solvent b used in the step (2) include a batch simple distillation apparatus, a vacuum distillation apparatus, a thin film distillation apparatus such as a flash evaporator, a rotary distillation apparatus, a stirring evaporator, and the like. From the viewpoint of well removing the organic solvent b, a rotary distillation apparatus and a stirring evaporation apparatus are preferable.
  • a rotary vacuum distillation apparatus such as a rotary evaporator is preferable, and among the stirring evaporators, a stirring tank thin film evaporator is preferable.
  • the temperature of the dispersion-treated product when removing the organic solvent b can be appropriately selected depending on the type of the organic solvent b to be used, but is preferably 20 ° C or higher, more preferably 25 ° C or higher, and more preferably 30 ° C or higher, under reduced pressure. And 80 degrees C or less is preferable, 70 degrees C or less is more preferable, and 65 degrees C or less is still more preferable.
  • the pressure at this time is preferably 0.01 MPa or more, more preferably 0.02 MPa or more, further preferably 0.05 MPa or more, more preferably 0.5 MPa or less, more preferably 0.2 MPa or less, and 0.1 MPa or less. Is more preferable.
  • the time for removing the organic solvent b is preferably 1 hour or longer, more preferably 2 hours or longer, still more preferably 5 hours or longer, preferably 24 hours or shorter, more preferably 12 hours or shorter, still more preferably 10 hours or shorter. .
  • the removal of the organic solvent b is preferably carried out until the solid content concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less. It is preferable to carry out until.
  • the obtained concentrate is preferably subjected to a centrifugal separation process to be separated into a liquid layer part and a solid part, and the liquid layer part is recovered.
  • the recovered liquid layer part is mainly a dispersion in which the pigment-containing polymer particles P are dispersed in water, and the solid part is mainly a solid content composed of coarse particles generated due to poor dispersion or aggregation. Accordingly, a pigment aqueous dispersion can be obtained from this liquid layer portion.
  • a moisturizer such as glycerin, an antiseptic, an antifungal agent and the like to the obtained pigment aqueous dispersion from the viewpoint of preventing drying and preventing spoilage.
  • the organic solvent b in the obtained pigment aqueous dispersion is preferably substantially removed, but may remain as long as the object of the present invention is not impaired.
  • the amount of the residual organic solvent b is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less.
  • the nonvolatile component concentration (solid content concentration) of the pigment aqueous dispersion of the obtained pigment-containing polymer particles P is 10 masses from the viewpoint of improving the dispersion stability of the pigment aqueous dispersion and facilitating the preparation of the water-based ink. % Or more is preferable, 15% by mass or more is more preferable, 30% by mass or less is preferable, and 25% by mass or less is more preferable.
  • the obtained pigment aqueous dispersion of the pigment-containing polymer particles P is obtained by dispersing the solid content of the pigment and the water-insoluble polymer p in water as a main medium.
  • the average particle diameter of the pigment-containing polymer particles P in the pigment water dispersion is to improve the dispersion stability of the pigment water dispersion and the storage stability of the water-based ink, and by suppressing the viscosity increase when the water-based ink is dried. From the viewpoint of improving dischargeability, 40 nm or more is preferable, 60 nm or more is more preferable, 80 nm or more is more preferable, 150 nm or less is preferable, and 140 nm or less is even more preferable.
  • the average particle size of the pigment-containing polymer particles P is measured by the method described in the examples.
  • the average particle diameter of the pigment-containing polymer particles P in the water-based ink using the pigment-containing polymer particles P is the same as the average particle diameter in the pigment water dispersion, and the preferred average particle diameter is in the form of pigment water dispersion. This is the same as the preferred embodiment of the average particle size in the body.
  • the content of the pigment-containing polymer particles P in the water-based ink accelerates the drying on the paper surface when printing on a low water-absorbing recording medium, and the ink in the drying process From the viewpoint of suppressing the reduction of the dot diameter of the toner, obtaining an image having excellent uniformity, and improving the printing density, it is preferably 1.4% by mass or more, more preferably 2.8% by mass or more, and still more preferably. 4.2% by mass or more.
  • the ink density at the time of solvent volatilization is lowered, the reduction of the ink dot diameter during the drying process when printing on a low water-absorbing recording medium is suppressed, and the printing density is increased from the viewpoint of obtaining an image with excellent uniformity.
  • it is preferably 21% by mass or less, more preferably 14% by mass or less, and still more preferably 8.4% by mass or less.
  • the content of the water-insoluble polymer p in the water-based ink improves the storage stability and dischargeability of the water-based ink, and during the drying process when printing on a low water-absorbing recording medium. From the viewpoint of suppressing the reduction of the dot diameter of the ink and obtaining an image having excellent uniformity, it is preferably 0.4% by mass or more, more preferably 0.8% by mass or more, and further preferably 1.2% by mass or more. is there.
  • the ink viscosity at the time of solvent volatilization is 6 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 2.4 mass% or less.
  • the surfactant used in the present invention is at least two of an acetylene glycol-based nonionic surfactant (A) having an HLB of 0 or more and 5 or less and a nonionic surfactant (B) having an HLB of 6 or more and 20 or less. It is.
  • the surfactant (A) used in the present invention is an acetylene glycol-based nonionic surfactant having an HLB of 0 or more and 5 or less.
  • Surfactant (A) improves the wetting and spreading properties of water-based ink, suppresses the reduction of the dot diameter of the ink during the drying process when printing on a low water-absorbing recording medium, and produces an image with excellent uniformity. Used to get.
  • the HLB of the surfactant (A) is preferably 5.0 or less, more preferably 4.9 or less, and still more preferably 4.8 or less.
  • the HLB of the surfactant (A) is preferably 2.0 or more, more preferably 2.5 or more, and still more preferably 2.8 or more, from the viewpoint of solubility in water-based ink.
  • Examples of the hydrophilic group contained in the surfactant include a hydroxyl group and an ethyleneoxy group.
  • the average addition mole number of ethylene oxide of the surfactant (A) (hereinafter also referred to as “EO average addition mole number”) is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less. More preferably, it is 1.5 or less.
  • Preferred examples of the surfactant (A) include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and Examples thereof include one or more acetylene glycols selected from 2,5-dimethyl-3-hexyne-2,5-diol, and ethylene oxide adducts of the acetylene glycols.
  • 2,4,7,9-tetramethyl-5-decyne-4,7 is considered from the viewpoint of improving the wet-spreading property of water-based ink and concealing property when printing on a low water-absorbing recording medium.
  • component (A) commercially available products of component (A) include Surfinol 104 (2,4,7,9-tetramethyl-5-decyne-4,7-diol, manufactured by Nissin Chemical Industry Co., Ltd. and Air ⁇ ⁇ Products & Chemicals, EO average added mole number: 0, HLB: 3.0), 104E (2,4,7,9-tetramethyl-5-decyne-4,7-diol diluted with ethylene glycol 50%), 104PG- 50 (2,4,7,9-tetramethyl-5-decyne-4,7-diol diluted with propylene glycol in 50%), Surfynol 420 (2,4,7,9-tetramethyl-5-decyne- EO average 1.3 mol adduct of 4,7-diol, HLB: 4.7), acetylenol E13T manufactured by Kawaken Fine Chemical Co., Ltd. (EO average addition mol number: 1.3, H
  • the content of the component (A) improves the wet-spreading property of the water-based ink and is preferably 0.4% by mass or more in the water-based ink from the viewpoint of concealability when printing on a low water-absorbing recording medium. Preferably it is 0.6 mass% or more, More preferably, it is 0.8 mass% or more. Further, the content of the component (A) is preferably from the viewpoint of improving the dischargeability of the water-based ink, improving the storage stability of the ink when printing on a low water-absorbing recording medium, and improving the storage stability of the ink. It is 4.0 mass% or less, More preferably, it is 3.0 mass% or less, More preferably, it is 2.8 mass% or less, More preferably, it is 2.0 mass% or less.
  • the surfactant (B) used in the present invention is a nonionic surfactant having an HLB of 6 or more and 20 or less.
  • the surfactant (B) is used for improving the solubility of the component (A) in the water-based ink and suppressing the turbidity of the ink.
  • the HLB of the surfactant (B) is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 13 or more, and from the viewpoint of ejection properties, It is 19 or less, more preferably 18.5 or less, still more preferably 17.5 or less, even more preferably 17 or less, even more preferably 16.5 or less, and even more preferably 16 or less.
  • the surfactant (B) include acetylene glycol ethylene oxide adducts, alcohol alkylene oxide adducts, fatty acid alkanolamides, and the like, but from acetylene glycol ethylene oxide adducts and alcohol alkylene oxide adducts. One or more selected are preferable.
  • the EO average addition mole number is preferably 5.0 or more, more preferably 6.0 or more, still more preferably 7.0 or more, still more preferably 8.0 or more, An ethylene oxide adduct that is preferably 40.0 or less, more preferably 38.0 or less, still more preferably 36.0 or less, even more preferably 34.0 or less, and even more preferably 32.0 or less is preferable.
  • Surfactant (B) can be obtained by subjecting acetylene glycol obtained by the same method as surfactant (A) to an addition reaction so that ethylene oxide has a desired number of additions.
  • an alkylene oxide adduct of alcohol having 6 to 30 carbon atoms is preferable from the viewpoint of improving the solubility of the component (A) in water-based ink and suppressing turbidity of the ink.
  • the alcohol has preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less. It is.
  • an ethylene oxide adduct, an adduct of ethylene oxide and propylene oxide is preferable, and an adduct of ethylene oxide is preferable.
  • R 3 O — [(EO) m / (PO) n] —H (2)
  • R 3 represents a hydrocarbon group having 6 to 30 carbon atoms
  • EO represents an ethyleneoxy group
  • PO represents a propyleneoxy group
  • m and n represent average added mole numbers
  • m is 4 to 100.
  • N is 0 or more and 50 or less
  • the sum of m and n is 4 or more and 120 or less
  • “/” indicates that EO and PO may be random or block, and the addition order of EO and PO is not limited.
  • the number of carbon atoms of the hydrocarbon group as R 3 is preferably 8 or more, more preferably 10 or more, and still more preferably from the viewpoint of improving the solubility of the component (A) in the water-based ink and suppressing turbidity of the ink. It is preferably 12 or less, more preferably 24 or less, more preferably from the viewpoint of concealing property when printing on a low water-absorbing recording medium and improving the storage stability of the ink. Is 22 or less, more preferably 20 or less, still more preferably 18 or less, and still more preferably 14 or less.
  • the hydrocarbon group is preferably a linear or branched alkyl group or alkenyl group, and is preferably a linear alkyl group or alkenyl group.
  • the hydrocarbon group having 6 to 30 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 2-propylheptyl group, and lauryl.
  • lauryl group, myristyl group, palmityl group, stearyl group, oleyl group, 2-octyldecyl group, behenyl group Are preferred, and a lauryl group is more preferred.
  • the average added mole number m of the ethyleneoxy group is 4 or more and 100 or less, the viewpoint of improving the solubility of the component (A) in the aqueous ink, suppressing the turbidity of the ink, and the viewpoint of improving the storage stability of the ink. Therefore, it is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and from the viewpoint of ejection properties, it is preferably 80 or less, more preferably 70 or less, still more preferably 60 or less, and even more preferably 50 or less. More preferably, it is 30 or less.
  • the average added mole number n of the propyleneoxy group is 0 or more and 50 or less, and n is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and still more, from the same viewpoint as described above. Preferably it is 5 or less, and more preferably 0.
  • the total amount of m and n is 4 or more and 120 or less, and from the same viewpoint as above, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, preferably 80 or less, more preferably 70 or less. More preferably, it is 60 or less, still more preferably 50 or less, and still more preferably 30 or less.
  • the compound of formula (1) may be a block body or a random body.
  • the hydroxy group side is preferably an oxyethylene chain, that is, RO- (PO) (EO) -H. Further, in the case of a block body, it may be a RO- (EO) (PO) (EO) -H triblock body.
  • alkylene oxide adducts of alcohol include Emulgen 108 (HLB: 12.1, EO average added moles: 6) and 109P (HLB: 13.5) manufactured by Kao Corporation as ethylene oxide adducts of lauryl alcohol. 6, EO average added mole number 8), 120 (HLB: 15.3, EO average added mole number: 13), 147 (HLB: 16.3, EO average added mole number: 17), 150 (HLB) : 18.4, EO average added mole number: 44).
  • Emulgen 707 manufactured by Kao Corporation (ethylene oxide adduct of secondary alcohol having 11 to 15 carbon atoms, HLB: 12.1, EO average added mole number: 6), 220 (directly having 16 to 18 carbon atoms)
  • An ethylene oxide adduct of a chain primary alcohol, HLB: 14.2, EO average addition mole number: 13) and the like can be mentioned.
  • the content of the component (B) improves the solubility of the component (A) in the water-based ink, suppresses turbidity of the ink, and suppresses uneven color when printed on a low water-absorbing recording medium. From the viewpoint of obtaining an image having excellent uniformity, it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and still more preferably 1.8% by mass or more. It is. In addition, the content of the component (B) improves the discharge performance of the water-based ink, suppresses uneven color when printed on a low water-absorbing recording medium, and obtains an image with excellent uniformity, and the ink.
  • it is preferably 9.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 5.0% by mass or less, still more preferably 4.5% by mass or less, and more. More preferably, it is 3.0 mass% or less.
  • the total content of the surfactants (A) and (B) in the water-based ink is preferably 1 from the viewpoint of suppressing the foaming of the water-based ink and improving the drive frequency response by suppressing an increase in ink viscosity.
  • 0.5% by mass or more more preferably 1.8% by mass or more, further preferably 2.0% by mass or more, and preferably 9.0% by mass or less, more preferably 6.0% by mass or less,
  • it is 5.0 mass% or less, More preferably, it is 4.0 mass% or less.
  • the surfactants (A) and (B) when the surfactants (A) and (B) are blended in the ink to prepare the water-based ink of the present invention, the surfactants (A) and (B) may be mixed and used in advance. it can. In that case, the compounding quantity of surfactant (A) and (B) becomes each content. And, it is a water-based ink in which surfactants (A) and (B) are mixed as a surfactant.
  • the mass ratio of the surfactant (A) to the surfactant (B) [surfactant (A) / surfactant (B)] is preferably 0 from the viewpoint of suppression of foaming of aqueous ink and drive frequency response. .1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.0 or less. .
  • the aqueous ink of the present invention may contain other surfactants other than the surfactants (A) and (B) as long as the effects of the present invention are not impaired.
  • the total content of the surfactant (A), the surfactant (B) and other surfactants in the water-based ink is preferably 1.5% by mass or more, more preferably 1.8% by mass or more, and still more preferably. Is 2.0% by mass or more, and preferably 10.0% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.5% by mass or less, and still more preferably 4.0% by mass. It is as follows.
  • the polyether-modified silicone (C) used in the present invention has a kinematic viscosity at 25 ° C. of 30 mm 2 / s to 190 mm 2 / s.
  • the modified silicone compound (C) is a water-based ink that suppresses the shrinkage of the dot diameter of the ink droplets during the drying process after the water-based ink has spread on the recording medium and concentrates the surfactant on the nozzle surface. It is used to suppress the drying of the ink and improve the dischargeability. From that viewpoint, the kinematic viscosity at 25 ° C.
  • the modified silicone compound (C) is preferably 40 mm 2 / s or more, more preferably 50 mm 2 / s or more, further preferably 60 mm 2 / s or more, and preferably It is 185 mm ⁇ 2 > / s or less, More preferably, it is 180 mm ⁇ 2 > / s or less, More preferably, it is 175 mm ⁇ 2 > / s or less, More preferably, it is 160 mm ⁇ 2 > / s or less, More preferably, it is 140 mm ⁇ 2 > / s or less.
  • the kinematic viscosity at 25 ° C. can be determined with an Ubbelohde viscometer.
  • the polyether-modified silicone (C) has a structure in which the side chain and / or terminal hydrocarbon group of the silicone oil is substituted with a polyether group.
  • Polyether groups of the polyether-modified silicone compound (C) include polyethyleneoxy group, polypropyleneoxy group, ethyleneoxy group (EO) and propyleneoxy group (trimethyleneoxy group or propane-1,2-diyloxy group; PO)
  • a polyalkyleneoxy group in which is added in a block shape or randomly, a compound in which a polyether group is grafted to a silicone main chain, a compound in which silicone and a polyether group are bonded in a block shape, or the like can be used.
  • Preferable examples of the polyether-modified silicone compound (C) include compounds represented by the following general formula (3) or (4).
  • R 5 represents an alkyl group having 1 to 3 carbon atoms or a hydroxy group
  • R 6 represents an alkanediyl group having 2 to 5 carbon atoms
  • R 7 represents a hydrogen atom
  • EO represents an ethyleneoxy group
  • PO represents a propyleneoxy group (trimethyleneoxy group or propane-1,2-diyloxy group)
  • a, b, c, and d represent the average addition of each unit A is 1 to 50
  • b is 0 to 10
  • c is 1 to 500
  • d is 1 to 50.
  • the plurality of R 5 may be the same or different.
  • a is preferably 1 to 30, more preferably 1 to 20, b is preferably 0 to 5, more preferably 0 to 3, and c is preferably 3 to 400, more preferably 5 to 300, and d is preferably 1 to 40, more preferably 1 to 30.
  • the a, b, c or d units may be the same or different.
  • the average added mole numbers a to d are preferably selected so that the kinematic viscosity at 25 ° C. of the compound represented by the general formula (3) is in the range of 30 mm 2 / s to 190 mm 2 / s.
  • R 5 , R 6 , R 7 , EO, PO, a, b and c are the same as described above.
  • E represents the average number of moles added of each unit and is 1 to 50.
  • R 5 , R 6 and R 7 may be the same or different.
  • a is preferably 1 to 30, more preferably 1 to 20
  • b is preferably 0 to 5, more preferably 0 to 3
  • c is preferably 1 to 400, more preferably 1 to 300
  • e is preferably 1 to 40, more preferably 1 to 30.
  • the a, b, c or e units may be the same or different.
  • the average addition mole numbers a, b, c and e are selected so that the kinematic viscosity at 25 ° C. of the compound represented by the general formula (4) is in the range of 30 mm 2 / s to 190 mm 2 / s. Is preferred.
  • polyether-modified silicone (C) examples include KF series manufactured by Shin-Etsu Chemical Co., Ltd .; KF-351 (kinematic viscosity at 25 ° C .: 70 mm 2 / s, the same shall apply hereinafter), KF-355A (kinematic viscosity: 150 mm) 2 / s), KF-642 (kinematic viscosity: 50 mm 2 / s), KF-945 (kinematic viscosity: 130 mm 2 / s), KF-6011 (kinematic viscosity: 130 mm 2 / s), KF-6015 (kinematic viscosity) : 130 mm 2 / s), KF-6204 (kinematic viscosity: 70 mm 2 / s), Sylface SAG series manufactured by Nissin Chemical Industry Co., Ltd .; Sylface SAG005 (kinematic viscosity: 170 mm 2 / s), SAG
  • the content of the polyether-modified silicone (C) in the water-based ink is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, and preferably Is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.3% by mass or less, and still more preferably 0. It is 2 mass% or less, More preferably, it is 0.1 mass% or less.
  • the mass ratio ⁇ [(A) + (B)] / (C) ⁇ of the total amount of the surfactant (A) and the surfactant (B) with respect to the amount of the polyether-modified silicone (C) is the water-based ink.
  • the water-based ink of the present invention preferably contains water-insoluble polymer particles from the viewpoint of fixability of printed matter printed on a low water-absorbing recording medium.
  • the nonionic surfactant (A), nonionic surfactant (B), and polyether-modified silicone (C) contained in the ink of the present invention improve the dispersion stability of insoluble polymer particles in water-based ink. Excellent dischargeability.
  • One embodiment of the water-insoluble polymer particles includes water-insoluble polymer particles that do not contain a pigment.
  • the water-based ink used in the present invention may contain water-insoluble polymer particles Q (hereinafter also referred to as “polymer particles Q”) from the viewpoint of fixability of printed matter printed on a low water-absorbing recording medium.
  • the polymer particles Q preferably do not contain a colorant from the viewpoint of improving the storage stability and dischargeability of the water-based ink.
  • the pigment-containing polymer particles P are used as the pigment, it is preferable to use the polymer particles Q in combination from the viewpoint of improving the storage stability and dischargeability of the water-based ink.
  • the polymer particles Q are preferably used as a dispersion containing the polymer particles Q from the viewpoint of improving the productivity of the water-based ink.
  • the water-insoluble polymer particles Q of the present invention are contained in an aqueous ink containing a structural unit derived from (meth) acrylic acid (q-1) and a structural unit derived from (meth) acrylic acid ester (q-2).
  • Water-insoluble polymer particles The glass transition temperature of the water-insoluble polymer particles is 10 ° C. or higher and 90 ° C. or lower,
  • the structural unit derived from the (meth) acrylic acid (q-1) is 1.0% by mass or more and 6.0% by mass or less in the total structural unit of the water-insoluble polymer particles.
  • the molar ratio of (meth) acrylic acid (q-1) and (meth) acrylic acid ester (q-2) introduced into the reaction system during the production of the water-insoluble polymer particles [(q-1) / (q- 2)] are water-insoluble polymer particles produced by increasing at least once during the reaction.
  • Examples of the monomer that provides the structural unit derived from (meth) acrylic acid (q-1) include acrylic acid and methacrylic acid, and methacrylic acid is preferred.
  • the content of the structural unit derived from (meth) acrylic acid (q-1) is determined from the viewpoint of improving the dispersion stability of the water-insoluble polymer particle Q, the storage stability of the ink, and the ejection property. Among them, 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 2.0% by mass or more, still more preferably 1.8% by mass or more, and 6.0% by mass or less. Preferably, it is 5.8 mass% or less, More preferably, it is 5.5 mass% or less, More preferably, it is 5.3 mass% or less.
  • content in a structural unit can be calculated from the preparation amount of the monomer at the time of manufacturing the polymer particle Q.
  • Examples of the monomer that provides the structural unit derived from the (meth) acrylic acid ester (q-2) include a (meth) acrylic acid ester containing an alkyl group and a (meth) acrylic acid ester containing an aromatic group.
  • the (meth) acrylic acid ester containing an alkyl group those having an alkyl group having 1 to 22 carbon atoms are preferable.
  • (meth) acrylic acid ester containing an aromatic group examples include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
  • a (meth) acrylic acid ester having an alkyl group preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms.
  • methyl methacrylate and 2-ethylhexyl acrylate are more preferred.
  • the content of the structural unit derived from the (meth) acrylic acid ester (q-2) is from the viewpoint of the fixing property of the ink film after drying, and suppresses the reduction of the dot diameter of the ink during the drying process, thereby making it uniform. From the viewpoint of obtaining an excellent image, in all the structural units of the polymer particles Q, preferably 94.0% by mass or more, more preferably 94.5% by mass or more, and 99.0% by mass or less, preferably Is 98.0 mass% or less.
  • the total content of the structural unit derived from (meth) acrylic acid (q-1) and the structural unit derived from (meth) acrylic acid ester (q-2) is the same as that described above.
  • a unit Preferably it is 95.0 mass% or more, More preferably, it is 96.0 mass% or more, More preferably, it is 98.0 mass% or more, and is 100.0 mass% or less.
  • the mass ratio [(q-1) / (q-2)] of the structural unit derived from (meth) acrylic acid (q-1) to the structural unit derived from (meth) acrylic acid ester (q-2) is From the same viewpoint, it is preferably 0.02 or more, more preferably 0.03 or more, still more preferably 0.04 or more, and preferably 0.20 or less, more preferably 0.15 or less, still more preferably. 0.10 or less.
  • the glass transition temperature of the polymer particles Q is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C. or higher, and still more preferably, from the viewpoint of image fixability. Is 45 ° C. or higher, and preferably 90 ° C. or lower, more preferably 85 ° C. or lower, still more preferably 80 ° C. or lower, and still more preferably 78 ° C. or lower.
  • the glass transition temperature of the polymer particles Q can be adjusted to a desired value by adjusting the type and composition ratio of monomers other than (meth) acrylic acid (q-1), for example, (q-2).
  • the polymer particles Q those appropriately synthesized may be used, or commercially available products may be used.
  • the polymer particles Q are produced by copolymerizing a mixture of (meth) acrylic acid (q-1) and (meth) acrylic acid ester (q-2) by a known polymerization method.
  • the polymerization method preferably includes an emulsion polymerization method and a suspension polymerization method, and more preferably an emulsion polymerization method.
  • a polymerization initiator can be used.
  • the polymerization initiator include persulfates and water-soluble azo polymerization initiators, and persulfates such as ammonium persulfate and potassium persulfate are preferable.
  • a surfactant can be used.
  • the surfactant examples include nonionic surfactants, anionic surfactants, and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of improving the dispersion stability of the resin particles.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, and the like, which improve the dispersion stability of resin particles. From the viewpoint, polyoxyethylene alkyl ether is preferable.
  • the polymerization temperature is preferably 50 ° C. or higher and 90 ° C. or lower
  • the polymerization time is preferably 1 hour or longer and 20 hours or shorter.
  • the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
  • the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation.
  • the obtained polymer can remove unreacted monomers and the like by reprecipitation, membrane separation, chromatographic method, extraction method and the like.
  • the polymer particles Q are preferably used as a polymer dispersion in which water is used as a dispersion medium without removing the solvent used in the polymerization reaction, from the viewpoint of compoundability in the ink.
  • the solid content concentration of the dispersion of the polymer particles Q is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 60% by mass or less, from the viewpoint of blending with the pigment-containing polymer particles P and the ink. More preferably, it is 50 mass% or less.
  • the weight average molecular weight of the polymer particles Q used in the present invention is excellent in uniformity from the viewpoint of fixability and suppresses the reduction of the ink dot diameter during the drying process when printed on a low water-absorbing medium. From the viewpoint of obtaining an image, it is preferably 100,000 or more, more preferably 200,000 or more, still more preferably 500,000 or more, preferably 2,500,000 or less, more preferably 1,000,000 or less. It is.
  • the average particle diameter of the polymer particles Q in the dispersion containing the polymer particles Q or in the water-based ink is from the viewpoint of improving the storage stability of the water-based ink and the printing density when printing on a low water-absorbing recording medium.
  • the thickness is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and still more preferably 130 nm or less.
  • the weight average molecular weight and average particle diameter of the polymer particles Q are measured by the methods described in the examples.
  • Examples of the dispersion of the commercially available polymer particles Q include acrylic resins such as “Neocryl A1127” (manufactured by DSM NeoResins, anionic self-crosslinking aqueous acrylic resin), “Joncrill 390” (manufactured by BASF Japan Ltd.), “ Urethane resins such as WBR-2018 and WBR-2000U (manufactured by Taisei Fine Chemical Co., Ltd.), styrene-butadiene resins such as SR-100 and SR102 (manufactured by Nippon A & L Co., Ltd.), Jonkrill 7100 ”,“ Johncrill 734 ”,“ Johncrill 538 ”(above, manufactured by BASF Japan Ltd.) and other styrene-acrylic resins, and“ Vinyl Blanc 701 ”(manufactured by Nissin Chemical Industry Co., Ltd.), etc.
  • acrylic resins such as “Neocryl A1127
  • Examples of the form of the polymer particles Q include a dispersion in which the polymer particles Q are dispersed in water, and may contain a dispersing agent such as a surfactant as necessary.
  • the dispersion of polymer particles Q fixes the ink droplets ejected from the inkjet nozzle to the recording medium, suppresses the reduction of the ink dot diameter during the drying process, and obtains an image with excellent uniformity. Also acts as an emulsion.
  • the content of the polymer particles Q in the dispersion containing the polymer particles Q is preferably 10% by mass or more, and more preferably 20% by mass or more from the viewpoint of dispersion stability of the polymer particles Q and convenience when blending the ink. 30 mass% or more is more preferable, 70 mass% or less is preferable, 60 mass% or less is more preferable, and 55 mass% or less is still more preferable.
  • the content of the polymer particles Q in the water-based ink suppresses the reduction of the dot diameter of the ink during the drying process when printing on a low-water-absorbing recording medium from the viewpoint of fixability.
  • it is 1.0% by mass or more, preferably 1.2% by mass or more, more preferably 1.4% by mass or more, and further preferably 1.6% by mass or more.
  • the mass ratio of pigment to water-insoluble polymer particles Q accelerates the drying of printed matter printed on a low water-absorbing recording medium, and suppresses the reduction of the ink dot diameter during the drying process.
  • the viewpoint of improving the print density, and the viewpoint of improving the fixability of the dry ink on the paper surface preferably 0.3 or more, more preferably 0.5 or more, More preferably, it is 0.7 or more, and preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.
  • the water-based ink of the present invention contains an organic solvent (D) from the viewpoint of improving image uniformity due to spreading of dots when printed on a low water-absorbing recording medium.
  • the content of the organic solvent (D) in the water-based ink is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 28% by mass or more, from the viewpoint of improving the ink dischargeability. Also, from the viewpoint of improving the storage stability of water-based inks, it accelerates the drying of printed matter printed on a low water-absorbing recording medium, suppresses the reduction of the ink dot diameter during the drying process, and has excellent uniformity. From the viewpoint of obtaining the above, it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less.
  • the organic solvent (D) contains one or more organic solvents having a boiling point of 90 ° C. or higher from the viewpoint of improving the drying property when printed on a low water-absorbing recording medium, and the boiling point of the organic solvent (D) is: It is 150 degreeC or more and 230 degrees C or less by the weighted average value weighted with content (mass%) of each organic solvent.
  • the organic solvent (D) it is preferable to use a plurality of organic solvents having different boiling points.
  • the weighted average value of the boiling points of the organic solvent (D) is 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of preventing the ink from drying in the inkjet nozzle. From the viewpoint of accelerating the drying property of the printed matter printed on the low water-absorbing recording medium, suppressing the reduction of the dot diameter of the ink in the drying process, and obtaining an image having excellent uniformity, preferably 230 ° C. or less, preferably It is 225 degrees C or less, More preferably, it is 215 degrees C or less, More preferably, it is 210 degrees C or less, More preferably, it is 200 degrees C or less.
  • An organic solvent having a lower boiling point has a higher saturated vapor pressure at a specific temperature and a higher evaporation rate.
  • the weighted average value of the boiling points of the organic solvent (D) is an index of the evaporation rate of the mixed solvent.
  • Examples of the compound used as the organic solvent (D) include polyhydric alcohols, polyhydric alcohol alkyl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, and the like. Storage stability and dischargeability of water-based inks From the viewpoint of improving the viscosity, one or more selected from polyhydric alcohols and polyhydric alcohol alkyl ethers are preferred, and polyhydric alcohols are more preferred. A plurality of polyhydric alcohols included in the concept of a polyhydric alcohol can be mixed and used, and a plurality of polyhydric alcohol alkyl ethers can also be mixed and used.
  • the content of one or more selected from polyhydric alcohol and polyhydric alcohol alkyl ether in the organic solvent (D) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. Substantially more preferably 100% by mass, still more preferably 100% by mass.
  • polyhydric alcohol examples include ethylene glycol (boiling point 197 ° C.), diethylene glycol (boiling point 244 ° C.), polyethylene glycol, propylene glycol (boiling point 188 ° C.), dipropylene glycol (boiling point 232 ° C.), polypropylene glycol, 1,3- Propanediol (boiling point 210 ° C.), 1,3-butanediol (boiling point 208 ° C.), 1,4-butanediol (boiling point 230 ° C.), 3-methyl-1,3-butanediol (boiling point 203 ° C.), 1, 5-pentanediol (boiling point 242 ° C), 1,6-hexanediol (boiling point 250 ° C), 2-methyl-2,4-pentanediol (boiling point 196 ° C
  • triethylene glycol (boiling point 285 ° C.), tripropylene glycol (boiling point 273 ° C.), glycerin (boiling point 290 ° C.) or the like is used in combination with a compound having a boiling point of less than 250 ° C., preferably a boiling point of less than 230 ° C. Can do.
  • ethylene glycol, propylene glycol, and diethylene glycol are preferable, and ethylene glycol and propylene glycol are more preferable from the viewpoints of dischargeability and drying on the paper surface when printing on a low water-absorbing recording medium.
  • polyhydric alcohol alkyl ether examples include ethylene glycol monoethyl ether (boiling point 135 ° C.), ethylene glycol monobutyl ether (boiling point 171 ° C.), diethylene glycol monomethyl ether (boiling point 194 ° C.), diethylene glycol monoethyl ether (boiling point 202 ° C.), Diethylene glycol monoisopropyl ether (boiling point 207 ° C), diethylene glycol monobutyl ether (boiling point 230 ° C), triethylene glycol monomethyl ether (boiling point 122 ° C), triethylene glycol monoisobutyl ether (boiling point 160 ° C), tetraethylene glycol monomethyl ether (boiling point 158) ° C), propylene glycol monoethyl ether (boiling point 133 ° C), dipropylene glycol monobutyl ether ( Point 1
  • Triethylene glycol monobutyl ether (boiling point: 276 ° C.) or the like can be used in combination with a compound having a boiling point of less than 250 ° C., preferably a compound having a boiling point of less than 230 ° C.
  • a compound having a boiling point of less than 250 ° C. preferably a compound having a boiling point of less than 230 ° C.
  • diethylene glycol monoisopropyl ether Dipropylene glycol monomethyl ether is preferred, and diethylene glycol monoisopropyl ether is more preferred.
  • nitrogen-containing heterocyclic compound examples include N-methyl-2-pyrrolidone (boiling point 202 ° C.), 2-pyrrolidone (boiling point 245 ° C.), 1,3-dimethylimidazolidinone (boiling point 220 ° C.), ⁇ -caprolactam ( Boiling point 136 ° C.).
  • the amide examples include formamide (boiling point 210 ° C.), N-methylformamide (boiling point 199 ° C.), N, N-dimethylformamide (boiling point 153 ° C.), and the like.
  • amines include monoethanolamine (boiling point 170 ° C.), diethanolamine (boiling point 217 ° C.), triethanolamine (boiling point 208 ° C.) and triethylamine (boiling point 90 ° C.).
  • sulfur-containing compound examples include dimethyl sulfoxide (boiling point 189 ° C.).
  • sulfolane (boiling point 285 ° C.) and thiodiglycol (boiling point 282 ° C.) can be used in combination with a compound having a boiling point of less than 250 ° C., preferably a compound having a boiling point of less than 230 ° C.
  • ethylene glycol when printing on a low water-absorbing recording medium, it contains one or more selected from ethylene glycol, propylene glycol, and diethylene glycol monoisopropyl ether from the viewpoint of ejection properties and ink drying properties on paper. It is preferable to contain at least one selected from ethylene glycol and propylene glycol.
  • the total content of ethylene glycol, propylene glycol and diethylene glycol monoisopropyl ether in the water-based ink is 15 masses from the viewpoint of ejection properties and ink drying properties on paper when printing on a low water-absorbing recording medium.
  • % Or more preferably 20% by weight or more, more preferably 23% by weight or more, and from the same viewpoint, 55% by weight or less is preferable, 45% by weight or less is more preferable, and 40% by weight or less is more preferable.
  • a combination of two or more polyhydric alcohols, a combination of two or more polyhydric alcohol alkyl ethers, and A combination of one or more polyhydric alcohols and one or more polyhydric alcohol alkyl ethers is preferred, a combination of one or more polyhydric alcohols and a combination of one or more polyhydric alcohols and one or more polyhydric alcohol alkyl ethers are more preferred.
  • the total content of propylene glycol and diethylene glycol in the water-based ink is preferably 15% by mass or more from the viewpoint of dischargeability and ink drying on the paper surface when printed on a low water-absorbing recording medium. More preferably, it is preferably at least 23% by mass, more preferably at least 23% by mass, and from the same viewpoint, it is preferably at most 55% by mass, more preferably at most 45% by mass, further preferably at most 40% by mass.
  • the content of propylene glycol in the water-based ink is preferably 10% by mass or more, more preferably 13% by mass or more, still more preferably 17% by mass or more, and preferably 55% by mass or less from the same viewpoint as above. 45 mass% or less is more preferable, and 40 mass% or less is still more preferable.
  • ⁇ Other ingredients Commonly used wetting agents, penetrating agents, dispersants, surfactants, viscosity modifiers, antifoaming agents, antiseptics, antifungal agents, rustproofing agents, and the like can be added to the water-based ink of the present invention.
  • the water-based ink of the present invention comprises a pigment aqueous dispersion, a nonionic surfactant (A), a nonionic surfactant (B), a polyether-modified silicone (C), an organic solvent (D), water, and as necessary.
  • the polymer particles Q and the like can be mixed and stirred.
  • the water content is preferably 20% by mass or more in the water-based ink from the viewpoint of improving the storage stability of the water-based ink and the viewpoint of improving the storage density of the water-based ink when printing on a low water-absorbing recording medium. More preferably, it is 30% by mass or more, and further preferably 40% by mass or more. Further, from the viewpoint of improving the ink dischargeability, it is preferably 75% by mass or less.
  • the pigment, polymer particles Q, organic solvent (D), and other components other than water are contained in the ink, a part of the water content can be replaced with other components and contained.
  • the viscosity at 32 ° C. of the water-based ink is preferably 2.0 mPa ⁇ s or more, more preferably 3.0 mPa ⁇ s or more, and even more preferably 5.0 mPa ⁇ s or more, from the viewpoint of improving the discharge property of the water-based ink. is there. Further, from the viewpoint of improving the storage stability and dischargeability of the water-based ink, it is preferably 12 mPa ⁇ s or less, more preferably 9.0 mPa ⁇ s or less, and even more preferably 7.0 mPa ⁇ s or less.
  • the pH of the water-based ink is preferably from the viewpoint of improving the storage stability and dischargeability of the water-based ink and from the viewpoint of improving the dot diameter spread, print density, and scratch resistance when printing on a low water-absorbing recording medium. Is 7.0 or more, more preferably 8.0 or more, and even more preferably 8.5 or more. Further, from the viewpoint of member resistance and skin irritation, the pH is preferably 11.0 or less, more preferably 10.0 or less, and even more preferably 9.5 or less.
  • the ink jet recording method of the present invention is an ink jet recording method for recording on a recording medium using the aqueous ink obtained above, and the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is as follows. 0 g / m 2 or more and 10 g / m 2 or less.
  • the ink jet recording apparatus there are a thermal type and a piezo type. In the present invention, the piezo type is more preferable.
  • the water absorption amount of the recording medium used in the present invention is 0 g / m 2 or more and 10 g / m 2 or less, preferably 0 g / m 2 or more and 6 g as the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water. / M 2 or less.
  • the said water absorption is measured by the method as described in an Example.
  • Examples of the recording medium used in the present invention include low water-absorbing coated paper and film.
  • the coated paper for example, general-purpose glossy paper “OK Top Coat Plus” (Oji Paper Co., Ltd., basis weight 104.7 g / m 2 , water absorption at a contact time of 100 milliseconds (the following water absorption is the same) 4.9 g / m 2), multicolored foam gloss paper (manufactured by Oji paper Co., Ltd., 104.7g / m 2, the water absorption amount 5.2g / m 2), UPMFinesse gloss (UPM Co., 115g / m 2, the water absorption 3.
  • general-purpose glossy paper “OK Top Coat Plus” Oji Paper Co., Ltd., basis weight 104.7 g / m 2 , water absorption at a contact time of 100 milliseconds (the following water absorption is the same) 4.9 g / m 2)
  • multicolored foam gloss paper manufactured by Oji paper Co., Ltd
  • UPM Finesse Matt manufactured by UPM, 115 g / m 2 , water absorption 4.4 g / m 2
  • TerraPress Silk manufactured by Stora Enso, 80 g / m 2 , water absorption 4.1 g / m 2
  • LumiArt manufactured by Stora Enso, 90 g / m 2
  • the film include a polyester film, a vinyl chloride film, a polypropylene film, a polyethylene film, and a nylon film. These films may be subjected to surface treatment such as corona treatment as necessary.
  • Examples of generally available films include Lumirror T60 (manufactured by Toray Industries, Inc., polyethylene terephthalate, thickness 125 ⁇ m, water absorption 2.3 g / m 2 ), PVC80BP (manufactured by Lintec Corporation, vinyl chloride, water absorption 1. 4 g / m 2 ), KAINUS KEE70CA (manufactured by Lintec Corporation, polyethylene), Yupo SG90 PAT1 (manufactured by Lintec Corporation, polypropylene), Bonile RX (manufactured by Kojin Film & Chemicals Co., Ltd., nylon) and the like.
  • Lumirror T60 manufactured by Toray Industries, Inc., polyethylene terephthalate, thickness 125 ⁇ m, water absorption 2.3 g / m 2
  • PVC80BP manufactured by Lintec Corporation, vinyl chloride, water absorption 1. 4 g / m 2
  • KAINUS KEE70CA manufactured by Lintec Corporation, polyethylene
  • the present invention further discloses the following water-based ink and ink jet recording method with respect to the above-described embodiments.
  • a water-based ink having a temperature of 230 ° C. or lower.
  • the content of the pigment in the water-based ink is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably
  • the water-based ink according to ⁇ 1> which is 10% by mass or less, more preferably 6% by mass or less.
  • ⁇ 3> The water-based ink according to ⁇ 1> or ⁇ 2>, wherein the pigment and the water-insoluble polymer p are in the form of water-insoluble polymer particles P containing the pigment.
  • the water-insoluble polymer p is represented by the structural unit derived from the ionic monomer (p-1), the structural unit derived from the hydrophobic monomer (p-2) having an aromatic ring, and the formula (1).
  • the water-based ink according to any one of the above ⁇ 1> to ⁇ 3>, which is a vinyl polymer containing one or more selected from structural units derived from a hydrophilic nonionic monomer (p-3).
  • the content of the structural unit derived from the ionic monomer (p-1) in the water-insoluble polymer p is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more.
  • the content of the structural unit derived from the hydrophobic monomer (p-2) having an aromatic ring in the water-insoluble polymer p is preferably 15% by mass or more, more preferably 30% by mass or more, and still more preferably 37 % By mass or more, more preferably 45% by mass or more, and preferably 84% by mass or less, more preferably 80% by mass or less, still more preferably 74% by mass or less, and still more preferably 70% by mass or less.
  • the content of the structural unit derived from the styrenic macromonomer in the water-insoluble polymer p is preferably 5% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably The water-based ink according to any one of ⁇ 4> to ⁇ 6>, wherein is 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
  • the content of the structural unit derived from the hydrophilic nonionic monomer (p-3) in the water-insoluble polymer p is preferably 13% by mass or more, more preferably 15% by mass or more, and further preferably 18% by mass or more. , More preferably 20% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 38% by mass or less, and still more preferably 35% by mass or less.
  • the water-based ink according to any one of 4> to ⁇ 7>.
  • the water-insoluble polymer p contains monomers (p-1), (p-2) and (p-3), and [[p-1) component / [(p-2) component + (p ⁇ 3)
  • the mass ratio of component]] is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.10 or more, and preferably 0.50 or less, more preferably 0.40.
  • the content of the water-insoluble polymer particles P containing the pigment in the water-based ink is preferably 1.4% by mass or more, more preferably 2.8% by mass or more, and further preferably 4.2% by mass or more.
  • the water-based ink according to any one of ⁇ 3> to ⁇ 9> which is preferably 21% by mass or less, more preferably 14% by mass or less, and still more preferably 8.4% by mass or less.
  • the content of the water-insoluble polymer p in the water-based ink is preferably 0.4% by mass or more, more preferably 0.8% by mass or more, still more preferably 1.2% by mass or more, and preferably
  • the HLB of the surfactant (A) is preferably 5.0 or less, more preferably 4.9 or less, still more preferably 4.8 or less, and preferably 2.0 or more, more preferably
  • the average added mole number of ethylene oxide of the surfactant (A) is preferably 0 or more, and preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less, The aqueous ink according to any one of ⁇ 1> to ⁇ 12>, more preferably 1.5 or less.
  • surfactant (A) is acetylene glycol having an average addition mole number of ethylene oxide of 0 to 3.0.
  • Surfactant (A) contains 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2 , 5-dimethyl-3-hexyne-2,5-diol, and one or more acetylene glycols selected from ethylene oxide adducts of acetylene glycol, preferably 2, 4, 7, 9 One or more selected from ethylene oxide adducts of tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol, more preferably The water-based ink according to any one of ⁇ 1> to ⁇ 13>, wherein the surfactant (A) is acetylene glycol having
  • the content of the surfactant (A) is preferably 0.4% by mass or more, more preferably 0.6% by mass or more, and still more preferably 0.8% by mass or more in the water-based ink. Preferably, it is 4.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.8% by mass or less, and still more preferably 2.0% by mass or less. > The water-based ink according to any one of the above.
  • the HLB of the surfactant (B) is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 13 or more, and preferably 19 or less, more preferably 18 Or less, more preferably 17.5 or less, even more preferably 17 or less, even more preferably 16.5 or less, and still more preferably 16 or less, according to any one of ⁇ 1> to ⁇ 16> above Water-based ink.
  • the surfactant (B) is at least one selected from an ethylene oxide adduct of acetylene glycol, an alkylene oxide adduct of alcohol, and a fatty acid alkanolamide, preferably an ethylene oxide adduct of acetylene glycol and an alcohol.
  • the water-based ink according to any one of ⁇ 1> to ⁇ 17>, which is at least one selected from alkylene oxide adducts.
  • the surfactant (B) is an ethylene oxide adduct of acetylene glycol having an average addition mole number of ethylene oxide of 5.0 to 40.0 and an alkylene oxide adduct of alcohol having 6 to 30 carbon atoms.
  • the surfactant (B) has an average addition mole number of ethylene oxide of preferably 5.0 or more, more preferably 6.0 or more, still more preferably 7.0 or more, and still more preferably 8.0 or more. And preferably 40.0 or less, more preferably 38.0 or less, even more preferably 36.0 or less, even more preferably 34.0 or less, and even more preferably 32.0 or less.
  • the surfactant (B) has 6 or more carbon atoms, preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and the number of carbon atoms is 30 or less, preferably 24 or less.
  • the content of the surfactant (B) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and still more preferably 1.8%. And preferably 9.0% by weight or less, more preferably 6.0% by weight or less, still more preferably 5.0% by weight or less, still more preferably 4.5% by weight or less, and even more preferably
  • the total content of the surfactants (A) and (B) in the water-based ink is preferably 1.5% by mass or more, more preferably 1.8% by mass or more, and further preferably 2.0% by mass.
  • Mass ratio of surfactant (A) to surfactant (B) [surfactant (A) / surfactant (B)] is preferably 0.1 or more, more preferably 0.2 or more. Any of the above ⁇ 1> to ⁇ 23>, more preferably 0.3 or more, and preferably 3.0 or less, more preferably 2.0 or less, and still more preferably 1.0 or less.
  • the total content of the surfactant (A), the surfactant (B) and other surfactants in the water-based ink is preferably 1.5% by mass or more, more preferably 1.8% by mass or more. More preferably, the content is 2.0% by mass or more, and preferably 10.0% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.5% by mass or less, and still more preferably 4.% by mass.
  • the water-based ink according to any one of ⁇ 1> to ⁇ 24>, which is 0% by mass or less.
  • a kinematic viscosity at 25 ° C. of the polyether-modified silicone (C) is preferably 40 mm 2 / s or more, more preferably 50 mm 2 / s or more, more preferably 60 mm 2 / s or more, and, preferably 185 mm 2 / s or less, more preferably 180 mm 2 / s or less, more preferably 175mm 2 / s or less, even more preferably 160 mm 2 / s or less, even more preferably at most 140 mm 2 / s, the ⁇ 1>
  • the aqueous ink according to any one of ⁇ 25>.
  • the content of the polyether-modified silicone (C) in the water-based ink is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.03% by mass or more. And preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.3% by mass or less, and still more preferably.
  • the water-based ink according to any one of ⁇ 1> to ⁇ 26>, wherein is 0.2% by mass or less, more preferably 0.1% by mass or less.
  • the mass ratio ⁇ [(A) + (B)] / (C) ⁇ of the total amount of the surfactant (A) and the surfactant (B) with respect to the amount of the polyether-modified silicone (C) is Preferably it is 0.5 or more, more preferably 1 or more, still more preferably 2.5 or more, even more preferably 5 or more, even more preferably 10 or more, still more preferably 20 or more, and preferably 400 or less.
  • ⁇ 29> The water-based ink according to any one of ⁇ 1> to ⁇ 28>, further comprising water-insoluble polymer particles.
  • the weighted average value of the boiling points of the organic solvent (D) is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and preferably 225 ° C. or lower, more preferably 215 ° C. or lower, still more preferably 210.
  • ⁇ 31> Any one of the above ⁇ 1> to ⁇ 30>, preferably containing at least one selected from ethylene glycol, propylene glycol and diethylene glycol monoisopropyl ether, more preferably at least one selected from ethylene glycol and propylene glycol Water-based ink according to crab.
  • the total content of ethylene glycol, propylene glycol and diethylene glycol monoisopropyl ether in the water-based ink is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 23% by mass or more, and
  • the aqueous ink according to ⁇ 30> preferably 55% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.
  • propylene glycol is 10% by mass or more, preferably 13% by mass or more, more preferably 17% by mass or more, and preferably 55% by mass or less, in water-based ink.
  • ⁇ 34> Use of the water-based ink according to any one of ⁇ 1> to ⁇ 33> as a water-based ink for inkjet printing.
  • the ink-jet recording method has a water absorption of 0 g / m 2 or more and 10 g / m 2 or less, preferably 0 g / m 2 or more and 6 g / m 2 or less.
  • Production Example 1 Production of water-insoluble polymer p solution
  • a monomer, a solvent (methyl ethyl ketone) and a polymerization chain transfer agent (2-mercaptoethanol) shown in “Initially charged monomer solution” in Table 1 are added and mixed. Gas replacement was performed to obtain an initially charged monomer solution.
  • the polymerization chain transfer agent was mixed to obtain a dripping monomer solution 1, which was then placed in the dropping funnel 1 and replaced with nitrogen gas.
  • the monomer, solvent, polymerization initiator, and polymerization chain transfer agent shown in “Drip monomer solution 2” in Table 1 are mixed to obtain a drop monomer solution 2, which is placed in the dropping funnel 2 and replaced with nitrogen gas. It was. Under a nitrogen atmosphere, the initially charged monomer solution in the reaction vessel was maintained at 77 ° C. with stirring, and the dropped monomer solution 1 in the dropping funnel 1 was gradually dropped into the reaction vessel over 3 hours. Subsequently, the dropping monomer solution 2 in the dropping funnel 2 was gradually dropped into the reaction vessel over 2 hours. After completion of dropping, the mixed solution in the reaction vessel was stirred at 77 ° C. for 0.5 hour.
  • a polymerization initiator solution in which 0.6 part of the polymerization initiator (V-65) was dissolved in 27.0 parts of methyl ethyl ketone was prepared, added to the mixed solution, and aged by stirring at 77 ° C. for 1 hour. .
  • the polymerization initiator solution was further prepared, added and aged for 5 times.
  • the reaction solution in the reaction vessel was maintained at 80 ° C. for 1 hour, and methyl ethyl ketone was added to obtain a solution of water-insoluble polymer p (solid content concentration: 40.8%).
  • the obtained water-insoluble polymer p had a weight average molecular weight of 52,700.
  • the obtained water-insoluble polymer p was dried at 105 ° C. for 2 hours, and the polymer having reached a constant weight was dissolved in water at 5 ⁇ 10 ⁇ 3 mass% (in terms of solid content concentration), and the average particle diameter was obtained.
  • Styrene macromer “AS-6 (S)” manufactured by Toa Gosei Co., Ltd. (effective component concentration 50 mass%, number average molecular weight 6000)
  • M-40G Methoxypolyethylene glycol monomethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-40G (average number of moles of ethylene oxide added: 4, terminal: methoxy group)
  • Production Example 2 (Production of water dispersion of water-insoluble polymer particles containing carbon black) (1) 157.6 g of the water-insoluble polymer p solution (solid concentration 40.8%) obtained in Production Example 1 was mixed with 60.4 g of methyl ethyl ketone (MEK) to obtain a MEK solution of the water-insoluble polymer p. .
  • MEK methyl ethyl ketone
  • the MEK solution of the water-insoluble polymer p is charged into a 2 L volume of the disper, and while stirring at 1400 rpm, 448.3 g of ion exchange water, 19.5 g of 5N aqueous sodium hydroxide, and 1.5 g of 25% aqueous ammonia.
  • 89g was added and it stirred at 70 degreeC for 1 hour. After cooling to 25 ° C., the mixture was filtered through the 5 ⁇ m filter, and ion-exchanged water was further added so that the solid content concentration was 22.0% by mass to obtain an aqueous dispersion of a water-insoluble polymer p containing a pigment.
  • the average particle diameter of the water-insoluble polymer particles P containing the pigment in the obtained aqueous dispersion was 90 nm.
  • Production Example 3 (Production of water-insoluble polymer particles Q)
  • a reaction vessel equipped with a dropping funnel 0.5 g of methacrylic acid, 14.5 g of methyl methacrylate, 5.0 g of 2-ethylhexyl acrylate, latem E-118B (11.1 g of sodium polyoxyethylene alkyl ether sulfate, Kao Corporation) (Manufactured, surfactant), 0.2 g of potassium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator and 282.8 g of ion-exchanged water are mixed and mixed, followed by nitrogen gas replacement, and initially charged monomer A solution was obtained.
  • Example 1 (Production of water-based ink) Using the aqueous dispersion of water-insoluble polymer particles containing carbon black obtained in Production Example 2 and the water-insoluble polymer particles Q obtained in Production Example 3, 4% by mass of pigment and water-insoluble polymer particles Q in the ink were used. Was blended with the following composition A so as to be 2.0% by mass, and the obtained mixed liquid was filtered through the 5 ⁇ m filter to obtain a water-based ink. The results are shown in Table 2.
  • composition A Water dispersion containing carbon black (solid content 22% by mass) 26.00 g Water-insoluble polymer particles Q (methyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer (hereinafter referred to as MMA / 2-EHA / MAA), solid content 40.0% by mass, average particle size 100 nm) 5.00 g Surfynol 104PG-50 (manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol (50%), propylene glycol (50%), effective fraction 50%) with an average addition mole number of oxyethylene of 0) 2.0 g Nonionic surfactant (A) 1.0g Nonionic surfactant (B) 2.0g Polyether-modified silicone (C) 0.05g Organic solvent (D): Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 30.00 g Ion exchange water (remainder: 34.95 g) was
  • Nonionic surfactant (A) S104: Surfynol 104; 2,4,7,9-tetramethyl-5-decyne-4,7-diol
  • S420 Surfynol 420; ethylene oxide (20%) adduct of Surfynol 104, average addition mole of ethylene oxide Number: 1.3
  • Nonionic surfactant (B) S465: Surfinol 465; Ethylene oxide (65%) addition product of Surfynol 104, Ethylene oxide average addition mole number: 10 S485: Surfynol 485; Surfoxide 103 adduct of ethylene oxide (85%), average added mole number of ethylene oxide: 33 E120: Emulgen 120, ethylene oxide adduct of lauryl alcohol, HLB: 15.3 E147: Emulgen 147, ethylene oxide adduct of lauryl alcohol, HLB: 16.3 E150: Emulgen 150, ethylene oxide adduct of lauryl alcohol, HLB: 18.4
  • the “Surfinol” series is manufactured by Nissin Chemical Industry Co., Ltd. and Air Products & Chemicals, and the “Emulgen” series is manufactured by Kao Corporation.
  • KF-6204 Kinematic viscosity: 70 mm 2 / s
  • HLB: 10 KF-351A Kinematic viscosity: 70 mm 2 / s
  • HLB: 12 ⁇ KF-642 Kinematic viscosity: 50 mm 2 / s
  • HLB: 12 KF-6011 Kinematic viscosity: 130 mm 2 / s
  • HLB: 12 KF-355A Kinematic viscosity: 150 mm 2 / s
  • HLB: 12 SAG005 manufactured by Nissin Chemical Industry Co., Ltd., Silface SAG005, kinematic viscosity: 170 mm 2 / s, HLB: 7 KF-354L: Kinematic viscosity: 200 mm 2 / s
  • HLB: 16 KF-640 Kinematic viscosity: 20 mm 2 / s
  • HLB: 12 KF-643 Kinematic viscosity: 70 mm 2 /
  • Example 2 water-based ink was used in the same manner as in Example 1 except that the polyether-modified silicone (C) KF-6204 was changed to KF-351A, KF-642, KF-6011, KF-355A, SAG005. Got.
  • C polyether-modified silicone
  • Example 7 A water-based ink was obtained in the same manner as in Example 1 except that S104 of the nonionic surfactant (A) was changed to S420 in Example 1.
  • Examples 8-11 A water-based ink was obtained in the same manner as in Example 1, except that S465 of the nonionic surfactant (B) was changed to E120, E147, S485, and E150.
  • Example 12 In Example 1, except that S465 of the nonionic surfactant (B) was changed to E147, and the humectant was changed from PG 30% by mass to PG 15% by mass and iPDG 15% by mass in the same manner as in Example 1, Ink was obtained.
  • Example 13 A water-based ink was obtained in the same manner as in Example 1 except that the moisturizing agent was changed from 30% by mass of PG to 30% by mass of iPDG in Example 1.
  • Examples 14-17 In the same manner as in Example 1, except that the blending amount of KF-6204 in Example 1 was changed from 0.05% by mass to 0.01% by mass, 0.5% by mass, 1% by mass, and 3% by mass. A water-based ink was obtained.
  • Example 1 As shown in Table 2, the type of the polyether-modified silicone (C) was changed, the polyether-modified silicone (C) was not added, and the nonionic surfactant (A) was changed to no addition. Ink was obtained.
  • Examples 18 to 22 and Comparative Examples 6 to 8 A water-based ink was obtained in the same manner as in Example 1 except that the organic solvent (D) was changed to that shown in Table 2 in Example 1.
  • Table 2 shows the results of the water-based ink obtained above.
  • the inks of Examples 1 to 17 are superior to the inks of Comparative Examples 1 to 5 in terms of ejection properties, and even during printing on a recording medium, particularly a low water-absorbing recording medium (coated paper). It can be seen that an image excellent in uniformity can be obtained by suppressing the reduction of the dot diameter of the ink.
  • an aqueous system that is excellent in ejection properties, suppresses the reduction of the ink dot diameter during the drying process even when printed on a recording medium, particularly a low water-absorbing recording medium, and provides an image with excellent uniformity.
  • An ink and an ink jet recording method using the water-based ink can be provided.

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne : une encre à base d'eau ayant d'excellentes propriétés de décharge, moyennant quoi la contraction du diamètre des points d'encre pendant la durée de séchage de ceux-ci est supprimée et une image ayant une excellente uniformité est obtenue même lorsque l'encre est imprimée sur un support d'impression à faible capacité d'absorption de l'eau ; et un procédé d'impression à jet d'encre utilisant l'encre à base d'eau. Cette encre à base d'eau contient un pigment, un polymère insoluble dans l'eau, un tensioactif non ionique (A) à base d'acétylène glycol ayant un HLB de 0 à 5, un agent tensioactif non ionique (B) ayant un HLB de 6 à 20, une silicone modifiée par polyéther (C) ayant une viscosité dynamique à 25 °C de 30 mm2/s à 190 mm2/s et un solvant inorganique (D), la valeur moyenne pondérée du point d'ébullition du solvant organique (D) allant de 150 °C à 230° C.
PCT/JP2015/085262 2014-12-26 2015-12-16 Encre à base d'eau WO2016104294A1 (fr)

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US15/539,370 US10316207B2 (en) 2014-12-26 2015-12-16 Water-based ink
EP15872863.4A EP3239255B1 (fr) 2014-12-26 2015-12-16 Encre à base d'eau
CN201580067619.7A CN107001835B (zh) 2014-12-26 2015-12-16 水性油墨
KR1020177016220A KR20170100506A (ko) 2014-12-26 2015-12-16 수계 잉크

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* Cited by examiner, † Cited by third party
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WO2016208719A1 (fr) * 2015-06-25 2016-12-29 花王株式会社 Encre à base d'eau
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WO2019004488A1 (fr) * 2017-06-28 2019-01-03 Ricoh Company, Ltd. Encre, ensemble encre, récipient pour encre, procédé de formation d'image et appareil de formation d'image
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WO2019235048A1 (fr) * 2018-06-08 2019-12-12 花王株式会社 Encre d'héliogravure aqueuse
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US11319454B2 (en) 2017-02-27 2022-05-03 Hewlett-Packard Development Company, L.P. Polyurethane-based binder dispersion

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JP2023008056A (ja) * 2021-07-05 2023-01-19 セイコーエプソン株式会社 インクジェットインク組成物及び記録方法
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JP7186324B1 (ja) * 2022-05-10 2022-12-08 サカタインクス株式会社 水性インクジェット用インク組成物、及び印刷物

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005097597A (ja) * 2003-09-02 2005-04-14 Seiko Epson Corp 水性インク
JP2006206688A (ja) * 2005-01-26 2006-08-10 Seiko Epson Corp インクジェット記録用インク組成物
JP2006282810A (ja) * 2005-03-31 2006-10-19 Seiko Epson Corp インク組成物、これを用いた記録方法、および記録物
JP2006282759A (ja) * 2005-03-31 2006-10-19 Seiko Epson Corp インク組成物、これを用いたインクジェット記録方法及び記録物
JP2006524269A (ja) * 2003-02-06 2006-10-26 ヒューレット−パッカード デベロップメント カンパニー エル．ピー． インクジェットインク用途のための低バルク密度、低表面誘電率のラテックスポリマー
JP2009155568A (ja) * 2007-12-27 2009-07-16 Kao Corp インクジェット記録用水分散体の製造方法
JP2010138332A (ja) * 2008-12-15 2010-06-24 Fujifilm Corp インク組成物、インクジェット記録方法、及び、印刷物
JP2010174141A (ja) * 2009-01-29 2010-08-12 Ricoh Co Ltd 記録用インク、インクカートリッジ、インクジェット記録装置、インクジェット記録方法
JP2011195763A (ja) * 2010-03-23 2011-10-06 Seiko Epson Corp 水性インク組成物及びこれを用いたインクジェット記録方式の印刷方法
JP2015124238A (ja) * 2013-12-25 2015-07-06 セイコーエプソン株式会社 インクジェット記録用インク組成物

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004018337A1 (de) 2004-04-15 2005-12-08 Pelikan Hardcopy Production Ag Wässrige Ink Jet-Tinte
JP2008266598A (ja) * 2007-03-15 2008-11-06 Seiko Epson Corp インク組成物、インクジェット記録方法及び記録物
CN102162192B (zh) 2010-02-18 2015-08-05 精工爱普生株式会社 喷墨印染用前处理剂和喷墨印染方法
EP2368948B1 (fr) 2010-03-23 2014-04-23 Seiko Epson Corporation Composition d'encre aqueuse et procédé d'impression au moyen d'un système d'enregistrement à jet d'encre utilisant la composition
JP5440794B2 (ja) * 2010-04-30 2014-03-12 ブラザー工業株式会社 インクカートリッジおよびインクジェット記録装置
JP2012246460A (ja) 2011-05-31 2012-12-13 Seiko Epson Corp インク組成物およびインクジェット記録方法
JP5741839B2 (ja) * 2011-06-01 2015-07-01 セイコーエプソン株式会社 インク組成物及びインクジェット記録方法
ES2581290T3 (es) * 2012-03-06 2016-09-05 Oce-Technologies B.V. Composición de tinta
JP6334917B2 (ja) 2013-12-27 2018-05-30 花王株式会社 インクジェット記録方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006524269A (ja) * 2003-02-06 2006-10-26 ヒューレット−パッカード デベロップメント カンパニー エル．ピー． インクジェットインク用途のための低バルク密度、低表面誘電率のラテックスポリマー
JP2005097597A (ja) * 2003-09-02 2005-04-14 Seiko Epson Corp 水性インク
JP2006206688A (ja) * 2005-01-26 2006-08-10 Seiko Epson Corp インクジェット記録用インク組成物
JP2006282810A (ja) * 2005-03-31 2006-10-19 Seiko Epson Corp インク組成物、これを用いた記録方法、および記録物
JP2006282759A (ja) * 2005-03-31 2006-10-19 Seiko Epson Corp インク組成物、これを用いたインクジェット記録方法及び記録物
JP2009155568A (ja) * 2007-12-27 2009-07-16 Kao Corp インクジェット記録用水分散体の製造方法
JP2010138332A (ja) * 2008-12-15 2010-06-24 Fujifilm Corp インク組成物、インクジェット記録方法、及び、印刷物
JP2010174141A (ja) * 2009-01-29 2010-08-12 Ricoh Co Ltd 記録用インク、インクカートリッジ、インクジェット記録装置、インクジェット記録方法
JP2011195763A (ja) * 2010-03-23 2011-10-06 Seiko Epson Corp 水性インク組成物及びこれを用いたインクジェット記録方式の印刷方法
JP2015124238A (ja) * 2013-12-25 2015-07-06 セイコーエプソン株式会社 インクジェット記録用インク組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3239255A4 *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10465083B2 (en) 2015-06-25 2019-11-05 Kao Corporation Inkjet printing method and water-based ink
WO2016208719A1 (fr) * 2015-06-25 2016-12-29 花王株式会社 Encre à base d'eau
US10655030B2 (en) 2015-06-25 2020-05-19 Kao Corporation Water-based ink
JP7326534B2 (ja) 2015-06-25 2023-08-15 花王株式会社 水性インク
JP7129019B2 (ja) 2015-06-25 2022-09-01 花王株式会社 インクジェット記録用インクセット
US10584252B2 (en) 2015-06-25 2020-03-10 Kao Corporation Inkjet printing method and water-based ink
JP2017008319A (ja) * 2015-06-25 2017-01-12 花王株式会社 水性インク
JP2022107611A (ja) * 2015-06-25 2022-07-22 花王株式会社 水性インク
CN109312180A (zh) * 2016-07-20 2019-02-05 惠普发展公司，有限责任合伙企业 喷墨墨水组
CN109312185A (zh) * 2016-07-20 2019-02-05 惠普发展公司，有限责任合伙企业 具有预处理固定液的喷墨墨水组
US11535764B2 (en) 2016-11-14 2022-12-27 Kao Corporation Aqueous gravure ink
WO2018088560A1 (fr) * 2016-11-14 2018-05-17 花王株式会社 Encre d'héliogravure aqueuse
EP3564347A4 (fr) * 2016-12-28 2020-08-19 Kao Corporation Détergent liquide pour encre aqueuse
US10981385B2 (en) 2016-12-28 2021-04-20 Kao Corporation Cleaning liquid for aqueous ink
US11319454B2 (en) 2017-02-27 2022-05-03 Hewlett-Packard Development Company, L.P. Polyurethane-based binder dispersion
CN110770308A (zh) * 2017-06-28 2020-02-07 株式会社理光 油墨、油墨组、油墨容器、成像方法和成像装置
US11499062B2 (en) 2017-06-28 2022-11-15 Ricoh Company, Ltd. Ink, ink set, ink container, image forming method, and image forming apparatus
WO2019004488A1 (fr) * 2017-06-28 2019-01-03 Ricoh Company, Ltd. Encre, ensemble encre, récipient pour encre, procédé de formation d'image et appareil de formation d'image
US11505709B2 (en) 2017-12-27 2022-11-22 Kao Corporation Aqueous ink
WO2019131598A1 (fr) 2017-12-27 2019-07-04 花王株式会社 Encre aqueuse
JP2019119787A (ja) * 2017-12-28 2019-07-22 花王株式会社 インクジェット記録用水系インク
WO2019131479A1 (fr) * 2017-12-28 2019-07-04 花王株式会社 Encre aqueuse pour enregistrement au jet d'encre
JP7191512B2 (ja) 2017-12-28 2022-12-19 花王株式会社 インクジェット記録用水系インク
JP2019210433A (ja) * 2018-06-08 2019-12-12 花王株式会社 水性グラビアインキ
WO2019235048A1 (fr) * 2018-06-08 2019-12-12 花王株式会社 Encre d'héliogravure aqueuse
JP7241474B2 (ja) 2018-06-08 2023-03-17 花王株式会社 水性グラビアインキ
US11952500B2 (en) 2018-06-08 2024-04-09 Kao Corporation Aqueous gravure printing ink

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CN107001835A (zh) 2017-08-01
EP3239255A4 (fr) 2018-05-23
JP6677376B2 (ja) 2020-04-08
EP3239255A1 (fr) 2017-11-01
EP3239255B1 (fr) 2019-08-07
CN107001835B (zh) 2020-10-20

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